Processing method, method of manufacturing semiconductor device, processing apparatus and program

Abstract

The step coverage performance of a film formed on a substrate including a groove can be improved. The process includes a process of forming a film on a substrate by performing a cycle comprising (a) a process of supplying a raw material gas to the substrate from the side of the substrate including a concave portion on the surface; and (b) a process of supplying a reaction gas to the substrate a predetermined number of times, wherein in (a), the raw material gas is supplied under conditions in which the amount of decomposition of the raw material gas increases with the passage of time when the processing temperature and processing pressure are constant, and among the raw materials supplied in (a), the raw materials gas is decomposed by colliding the gas in a state in which the decomposed raw materials gas is 0% or more and within 1% with the inner wall of the concave portion to generate an intermediate, and the intermediate is attached to the inner wall of the concave portion, and in (b), the intermediate attached to the concave portion is reacted with the reaction gas.

Description

Technology Field

[0001] The present disclosure relates to a processing method, a method for manufacturing a semiconductor device, a processing device, and a program. Background Technology

[0002] Patent Document 1 discloses a technique in which, as a process of manufacturing a semiconductor device, an inert gas or a hydrogen-containing gas is supplied toward a substrate along with a raw gas, thereby making the flow rate of the raw gas flowing in a direction parallel to the surface of the substrate greater than the flow rate of the inert gas flowing in a direction parallel to the surface of the substrate in a process of purging the inside of a processing vessel. Prior art literature

[0003] 1. Japanese Patent Publication No. 2011-129879 The problem to be solved

[0004] Recently, due to the reduction in cell area caused by device miniaturization, the aspect ratio of recesses, such as grooves formed on the substrate, has increased. Consequently, there is a growing need to improve step coverage performance, such as film deposition on substrates containing deeper recesses. To improve step coverage performance, it is necessary to supply sufficient gas to the lower part of the recesses. However, if one attempts to supply sufficient gas to the lower part of the recesses due to the increased aspect ratio, the upper part of the device becomes over-treated with gas, and step coverage performance does not improve. Therefore, to improve step coverage performance, it is necessary to supply sufficient gas to the lower part of the recesses while suppressing the amount of treated gas supplied to the upper part of the device.

[0005] The present disclosure aims to provide a technology capable of improving the step coverage performance of a film formed on a substrate including a portion. means of solving the problem

[0006] According to one embodiment of the present disclosure, a process for forming a film on a substrate is provided by performing a cycle comprising: (a) supplying a raw material gas to a substrate from the side of a substrate having a recess on its surface; and (b) supplying a reaction gas to the substrate a predetermined number of times. In (a), the raw material gas is supplied under conditions in which the amount of decomposition of the raw material gas increases over time when the processing temperature and processing pressure are constant. Among the raw materials supplied in (a), the raw material gas is decomposed by colliding the gas in a state in which the decomposed raw material gas is 0% or more and within 1% with the inner wall of the recess to generate an intermediate, and the intermediate is attached to the inner wall of the recess. In (b), the intermediate attached to the recess is reacted with the reaction gas. Effects of the invention

[0007] According to the present disclosure, the step coverage performance of a film formed on a substrate including a portion can be improved. Brief explanation of the drawing

[0008] FIG. 1 is a longitudinal cross-sectional view illustrating a schematic of a substrate processing apparatus in one embodiment of the present disclosure. FIG. 2 is a cross-sectional view illustrating the details of the substrate support portion in FIG. 1. FIG. 3 (A) is a drawing illustrating a first gas supply system in one embodiment of the present disclosure, FIG. 3 (B) is a drawing illustrating a second gas supply system in one embodiment of the present disclosure, and FIG. 3 (C) is a drawing illustrating a third gas supply system in one embodiment of the present disclosure. FIGS. 4 (A) to FIGS. 4 (C) are drawings illustrating examples of chemical structural formulas of a first gas in one embodiment of the present disclosure. FIG. 5 (A) is a drawing illustrating a processing room exhaust system in one embodiment of the present disclosure, FIG. 5 (B) is a drawing illustrating a material room exhaust system in one embodiment of the present disclosure. FIG. 6 is a schematic configuration diagram of a controller of a substrate processing device in one embodiment of the present disclosure, and is a diagram illustrating the control system of the controller as a block diagram. FIG. 7 is a drawing illustrating a substrate processing sequence in one embodiment of the present disclosure. FIG. 8 is a schematic diagram illustrating the state of the substrate surface during the first gas supply in one embodiment of the present disclosure. FIG. 9 is a diagram illustrating the relationship between the supply time and decomposition amount of a first gas in one embodiment of the present disclosure. Specific details for implementing the invention

[0009] The following description refers to FIGS. 1 to 7. Furthermore, all drawings used in the following description are schematic, and the dimensional relationships of each element and the ratios of each element shown in the drawings do not necessarily correspond to reality. Additionally, the dimensional relationships of each element and the ratios of each element do not necessarily correspond to one another among multiple drawings.

[0010] (1) Configuration of the substrate processing device

[0011] The configuration of the substrate processing device (10) is explained using Fig. 1.

[0012] The substrate processing device (10) is provided with a reaction tube containment chamber (206b), a cylindrical reaction tube (210) extending vertically within the reaction tube containment chamber (206b), a heater (211) as a heating unit [furnace body] installed on the outer circumference of the reaction tube (210), a gas supply structure (212) as a gas supply unit, and a gas exhaust structure (213) as a gas exhaust unit. The gas supply unit may include an upstream rectifier (214) or nozzles (223, 224) described later. Additionally, the gas exhaust unit may include a downstream rectifier (215) described later.

[0013] A gas supply structure (212) is installed upstream of the gas flow direction of the reaction tube (210), and gas is supplied into the reaction tube (210) from the gas supply structure (212), and gas is supplied from a horizontal direction with respect to the substrate (S). A gas exhaust structure (213) is installed downstream of the gas flow direction of the reaction tube (210), and gas inside the reaction tube (210) is discharged from the gas exhaust structure (213). The gas supply structure (212), the reaction tube (210), and the gas exhaust structure (213) are connected in a horizontal direction.

[0014] An upstream rectifier (214) is installed on the upstream side of the reaction pipe (210) between the reaction pipe (210) and the gas supply structure (212) to regulate the flow of gas supplied from the gas supply structure (212). Additionally, a downstream rectifier (215) is installed on the downstream side of the reaction pipe (210) between the reaction pipe (210) and the gas exhaust structure (213) to regulate the flow of gas discharged from the reaction pipe (210). The lower end of the reaction pipe (210) is supported by a manifold (216).

[0015] The reaction tube (210), upstream rectifier (214), and downstream rectifier (215) have a continuous structure and are formed of a material such as quartz or SiC. These are composed of a heat-transmitting member that transmits heat radiated from the heater (211). The heat from the heater (211) heats the substrate (S) or the gas.

[0016] The gas supply structure (212) includes a distribution section (225) that distributes gas supplied from each gas supply pipe, along with connecting gas supply pipes (251) and gas supply pipes (261). A plurality of nozzles (223) and nozzles (224) are installed on the downstream side of the distribution section (225). As described later, the gas supply pipes (251) and gas supply pipes (261) supply different types of gas. The nozzles (223) and nozzles (224) are arranged in a vertical relationship or in a horizontally parallel relationship. In this form, the gas supply pipes (251) and gas supply pipes (261) are collectively referred to as the gas supply pipe (221). Each nozzle is also referred to as a gas discharge section.

[0017] The distribution section (225) is configured to supply gas from the gas supply pipe (251) to the nozzle (223) and from the gas supply pipe (261) to the nozzle (224), respectively. For example, a path for gas flow is configured for each combination of gas supply pipe and nozzle. By doing so, the gas supplied from each gas supply pipe is not mixed, and thus, the generation of particles that may occur due to gas mixing in the distribution section (225) can be suppressed.

[0018] The upstream rectification section (214) includes a bulb (227) and a partition plate (226). The partition plate (226) extends in a horizontal direction. The horizontal direction referred to here indicates the direction of the side wall of the bulb (227). Multiple partition plates (226) are arranged in a vertical direction. The partition plates (226) are fixed to the side wall of the bulb (227) and configured so that gas does not move beyond the partition plate (226) to an adjacent area below or above. By preventing it from going over, the gas flow described later can be reliably formed.

[0019] The partition plate (226) is extended in the horizontal direction and has a continuous structure without holes. Each partition plate (226) is installed at a position corresponding to each substrate (S). Nozzles (223) and nozzles (224) are installed between the partition plates (226) or between the partition plates (226) and the light body (227).

[0020] The gas discharged from the nozzle (223) and nozzle (224) is supplied to the surface of the substrate (S) after the flow of the gas is organized by the partition plate (226). That is, when viewed from the substrate (S), the gas is supplied from the horizontal direction of the substrate (S). Since the partition plate (226) is extended in the horizontal direction and has a continuous structure without holes, the movement of the main stream of gas in the vertical direction is suppressed and it moves in the horizontal direction. Therefore, the pressure loss of the gas reaching each substrate (S) can be made uniform over the vertical direction.

[0021] The downstream rectifier (215) is configured such that its ceiling is higher than that of the substrate (S) placed at the top while the substrate (S) is supported on the substrate support (300) described later, and its bottom is lower than that of the substrate (S) placed at the bottom of the substrate support (300).

[0022] The downstream rectification section (215) includes a mineral body (231) and a partition plate (232). The partition plate (232) is extended in a horizontal direction. The horizontal direction referred to here indicates the direction of the side wall of the mineral body (231). Additionally, the partition plate (232) is arranged in multiple vertical directions. The partition plate (232) is fixed to the side wall of the mineral body (231) and configured so that gas does not move beyond the partition plate (232) to an adjacent area below or above. By preventing it from going over, the gas flow described later can be reliably formed. A flange (233) is installed on the side of the mineral body (231) that contacts the gas exhaust structure (213).

[0023] The partition plate (232) is extended in the horizontal direction and has a continuous structure without any holes. Each partition plate (232) is positioned corresponding to the substrate (S) and is installed at a position corresponding to each partition plate (226). It is preferable that the corresponding partition plate (226) and the partition plate (232) have equal heights. Additionally, when processing the substrate (S), it is preferable to match the height of the substrate (S) with the heights of the partition plate (226) and the partition plate (232). By making the structure this way, a horizontal flow is formed in which the gas supplied from each nozzle passes over the partition plate (226), the substrate (S), and the partition plate (232), as indicated by the arrows in the drawing. By making the partition plate (232) structure this way, the pressure loss of the gas discharged from each substrate (S) can be made uniform. Therefore, the gas flow passing through each substrate (S) is formed in a horizontal direction toward the gas exhaust structure (213) while the vertical flow is suppressed.

[0024] By installing partition plates (226) and partition plates (232), the pressure loss in the vertical direction can be made uniform at the upstream and downstream of each substrate (S), respectively, so a horizontal gas flow can be reliably formed across the partition plates (226), the substrate (S), and the partition plates (232) with the flow in the vertical direction suppressed.

[0025] The gas exhaust structure (213) is installed downstream of the downstream rectification section (215). The gas exhaust structure (213) is mainly composed of an ore body (241) and a gas exhaust pipe connection section (242). A flange (243) is installed on the downstream rectification section (215) side of the ore body (241). Since the gas exhaust structure (213) is made of metal and the downstream rectification section (215) is made of quartz, the flange (233) and the flange (243) are fixed with screws or the like by interposing a cushioning material such as an O-ring. It is preferable that the flange (243) be positioned on the outside of the heater (211) so that the influence of the heater (211) on the O-ring can be suppressed.

[0026] The gas exhaust structure (213) communicates with the space of the downstream rectification section (215). The light body (231) and the light body (241) have a continuous height structure. The ceiling of the light body (231) is configured to have a height equal to the ceiling of the light body (241), and the bottom of the light body (231) is configured to have a height equal to the bottom of the light body (241). An exhaust hole (244) is formed on the downstream side of the light body (241), either on the lower side or in the horizontal direction. The gas exhaust structure (213) is installed in the horizontal direction of the reaction tube (210) and is a horizontal exhaust structure that exhausts gas from the horizontal direction of the substrate (S).

[0027] The gas passing through the downstream rectification section (215) is exhausted from the exhaust port (244). At this time, since the gas exhaust structure (213) does not have a configuration such as a partition plate, a gas flow including a vertical direction is formed toward the exhaust port (244).

[0028] The material room (217) is installed in the lower part of the reaction tube (210) via a manifold (216). In the material room (217), a substrate (S) is placed (mounted) onto a substrate support (hereinafter sometimes simply referred to as a boat) (300) by a vacuum transport robot via a substrate inlet, or the substrate (S) is removed from the substrate support (300) by a vacuum transport robot.

[0029] Inside the material chamber (217), a substrate support member (300), a partition plate support member (310), and a vertical driving mechanism (400) constituting a first driving unit that drives the substrate support member (300) and the partition plate support member (310) (collectively referred to as substrate support members) in the vertical and rotational directions can be housed. In FIG. 1, the substrate support member (300) is shown in a state where it is raised by the vertical driving mechanism (400) and housed within the reaction tube (210).

[0030] The vertical driving mechanism (400) constituting the first driving unit is equipped with a vertical driving motor (410) as a driving source, a rotary driving motor (430), and a boat vertical mechanism (420) equipped with a linear actuator as a substrate support lifting mechanism that drives the substrate support (300) in the vertical direction.

[0031] The vertical driving motor (410) serving as the lifting mechanism for the partition plate support moves the nut (412), which is threaded onto the ball screw (411), up and down along the ball screw (411) by rotating the ball screw (411). By doing so, the partition plate support (310) and the substrate support (300), together with the base plate (402) that fixes the nut (412), are driven in the vertical direction between the reaction tube (210) and the material chamber (217). The base plate (402) is also fixed to the ball guide (415) which is engaged with the guide shaft (414), and is configured to move smoothly in the vertical direction along the guide shaft (414). The upper and lower ends of the ball screw (411) and the guide shaft (414) are respectively fixed to the fixing plate (413) and the fixing plate (416).

[0032] A boat up and down mechanism (420) equipped with a rotary drive motor (430) and a linear actuator constitutes a second drive unit and is fixed to a base flange (401) as an entity supported by a side plate (403) on a base plate (402).

[0033] The rotary drive motor (430) drives a rotary transmission belt (432) engaged with a tooth portion (431) installed at the tip portion, and rotates a support member (440) engaged with the rotary transmission belt (432). The support member (440) supports the partition plate support portion (310) at the base portion (311), and rotates the partition plate support portion (310) and the substrate support member (300) by being driven by the rotary drive motor (430) via the rotary transmission belt (432).

[0034] A boat up and down mechanism (420) equipped with a linear actuator drives the shaft (421) in the up and down direction. A plate (422) is installed at the tip portion of the shaft (421). The plate (422) is connected to a support member (441) fixed to the base (301) of the substrate support member (300) via a bearing member (423). By connecting the support member (441) to the plate (422) via the bearing member (423), when the partition plate support member (310) is rotated by a rotational driving motor (430), the substrate support member (300) can also rotate together with the partition plate support member (310).

[0035] Meanwhile, the support member (441) is supported on the support member (440) via a linear guide bearing (442). By making this configuration, when the shaft (421) is driven in the up and down direction by the boat up and down mechanism (420) equipped with a linear actuator, the support member (441) fixed to the substrate support member (300) can be driven in the up and down direction relative to the support member (440) fixed to the partition plate support member (310).

[0036] The support member (440) fixed to the partition plate support member (310) and the support member (441) fixed to the substrate support member (300) are connected by a vacuum bellows (443).

[0037] An O-ring (446) for vacuum sealing is installed on the upper surface of the base flange (401) as an individual unit, and as shown in FIG. 1, the upper surface of the base flange (401) is driven by an upper and lower driving motor (410) to raise it to a position where it is pressed against the material chamber (217), thereby maintaining a hermetic seal inside the reaction tube (210).

[0038] Next, details of the substrate support section will be described using FIGS. 1 and 2. The substrate support section is composed of a substrate support member (300) that supports at least a substrate (S) and is housed within a reaction tube (210). A substrate (S) is placed directly below the inner wall of the top plate of the reaction tube (210). Additionally, the substrate support section performs the transfer and replacement of the substrate (S) by a vacuum transport robot through a substrate inlet (not shown) inside the material transfer room (217), or transports the transferred and replaced substrate (S) into the reaction tube (210) to perform a process of forming a thin film on the surface of the substrate (S). The substrate inlet is installed, for example, on the side wall of the material transfer room (217). Additionally, the substrate support section may be considered to include a partition plate support section (310).

[0039] In the partition plate support section (310), a plurality of circular partition plates (314) are fixed at a predetermined pitch to a support (313) supported between a base (311) and a top plate (312). The substrate support section (300) includes a configuration in which a plurality of support rods (315) are supported on a base (311), and a plurality of substrates (S) are supported at a predetermined interval by these plurality of support rods (315).

[0040] In the substrate support member (300), a plurality of substrates (S) are placed at predetermined intervals by a plurality of support rods (315) supported by a base (311). The spaces between the plurality of substrates (S) supported by these support rods (315) are separated by circular partition plates (314) fixed (supported) at predetermined intervals by a support member (313) supported by a partition plate support member (310). Here, the partition plates (314) are placed directly below the substrates (S) and are placed on either the upper or lower side of the substrates (S), or both sides. The partition plates (314) block the space of each substrate (S).

[0041] The predetermined spacing of a plurality of substrates (S) placed on the substrate support (300) is equal to the upper and lower spacing of the partition plate (314) fixed to the partition plate support (310). In addition, the diameter of the partition plate (314) is formed to be larger than the diameter of the substrate (S).

[0042] The substrate support member (300) supports multiple substrates (S), for example, five substrates, in a vertical direction (vertical direction) in multiple stages using multiple support rods (315). The base (311), partition plate (314), and multiple support rods (315) are formed from materials such as quartz or SiC. In addition, although an example is presented here in which five substrates (S) are supported on the substrate support member (300), it is not limited thereto. For example, the substrate support member (300) may be configured to support approximately 5 to 50 substrates (S). Also, the partition plate (314) of the partition plate support member (310) is also called a separator.

[0043] The partition plate support (310) and the substrate support (300) are driven by an up-and-down driving mechanism (400) in the up-and-down direction between the reaction tube (210) and the material chamber (217) and in the rotational direction around the center of the substrate (S) supported by the substrate support (300).

[0044] Next, details of the gas supply system will be explained using FIGS. 3 (A) to FIGS. 3 (C). As shown in FIGS. 3 (A), the gas supply pipe (251) is equipped with a first gas source (252), a mass flow controller (MFC) (253) which is a flow rate controller (flow rate control unit), and a valve (254) which is an opening and closing valve, in order from the upstream direction.

[0045] The first gas source (252) is a first gas source containing a first element (also called a "first element-containing gas"). The first gas is one of the raw gas, that is, the processing gas. Here, the first gas is a gas in which at least two silicon atoms (Si) are bonded, such as a gas containing Si and chlorine (Cl), and is a raw gas containing Si-Si bonds, such as the hexachlorodisilane (Si2Cl6, hexachlorodisilane, abbreviated as HCDS) gas described in (A) of FIG. 4. As shown in (A) of FIG. 4, the HCDS gas contains Si and a chloro group (chloride) in its chemical structural formula (in one molecule).

[0046] This Si-Si bond has enough energy to be broken down by colliding with the wall constituting the main part of the substrate (S) described later within the reaction tube (210). Here, "breaking down" means that the Si-Si bond is severed. That is, the Si-Si bond is severed by colliding with the wall.

[0047] The first gas supply system (250) (also referred to as a silicon-containing gas supply system) is mainly composed of a gas supply pipe (251), an MFC (253), and a valve (254).

[0048] A gas supply pipe (255) is connected to the downstream side of the valve (254) in the gas supply pipe (251). In the gas supply pipe (255), an inert gas source (256), an MFC (257), and a valve (258), which is an opening and closing valve, are installed in order from the upstream direction. An inert gas, such as nitrogen (N2) gas, is supplied from the inert gas source (256).

[0049] The first inert gas supply system is mainly configured by a gas supply pipe (255), an MFC (257), and a valve (258). The inert gas supplied from the inert gas source (256) acts as a purge gas to purge the gas remaining in the reaction pipe (210) during the substrate processing process. The first inert gas supply system may be added to the first gas supply system (250).

[0050] Here, HCDS gas has been described as an example of the first gas, but it is not limited to this as long as it contains silicon and also contains Si-Si bonds; for example, 1,1,2,2-tetrachloro-1,2-dimethyldisilane [(CH3)2Si2Cl4, abbreviated: TCDMDS] or 1,2-dichloro-1,1,2,2-tetramethyldisilane [(CH3)4Si2Cl2, abbreviated: DCTMDS] may be used. As shown in FIG. 4 (B), TCDMDS contains Si-Si bonds and also contains chloro groups and alkylene groups. Additionally, as shown in FIG. 4 (C), DCTMDS contains Si-Si bonds and also contains chloro groups and alkylene groups.

[0051] As shown in Fig. 3 (B), the gas supply pipe (261) is equipped with a second gas source (262), an MFC (263) which is a flow controller (flow control unit), and a valve (264) which is an opening and closing valve, in order from the upstream direction.

[0052] The second gas source (262) is a second gas source containing a second element (hereinafter also referred to as "second element-containing gas"). The second gas is a gas different from the first gas and is one of the processing gases. Additionally, the second gas may be considered as a reaction gas or a reforming gas.

[0053] Here, the second gas contains a second element different from the first gas. The second element is, for example, any one of oxygen (O), nitrogen (N), or carbon (C). In this form, the second gas is, for example, a nitrogen-containing gas and is a hydrogen nitride-based gas containing NH bonds, such as ammonia (NH3), diazene (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas.

[0054] The second gas supply system (260) is mainly composed of a gas supply pipe (261), an MFC (263), and a valve (264).

[0055] A gas supply pipe (265) is connected to the downstream side of the valve (264) in the gas supply pipe (261). In the gas supply pipe (265), an inert gas source (266), an MFC (267), and a valve (268), which is an opening and closing valve, are installed in order from the upstream direction. An inert gas, such as nitrogen (N2) gas, is supplied from the inert gas source (266).

[0056] The second inert gas supply system is mainly configured by a gas supply pipe (265), an MFC (267), and a valve (268). The inert gas supplied from the inert gas source (266) acts as a purge gas to purge the gas remaining in the reaction pipe (210) during the substrate processing process. The second inert gas supply system may be added to the second gas supply system (260).

[0057] As shown in (C) of FIG. 3, a third gas source (272), an MFC (273) which is a flow controller (flow control unit), and a valve (274) which is an opening and closing valve are installed in the gas supply pipe (271) in order from the upstream direction. The gas supply pipe (271) is connected to the material room (217). When the material room (217) is made into an inert gas atmosphere or the material room (217) is made into a vacuum state, an inert gas is supplied.

[0058] The third gas source (272) is an inert gas source. The third gas supply system (270) is mainly composed of a gas supply pipe (271), an MFC (273), and a valve (274). The third gas supply system is also called a gas supply system.

[0059] Next, the exhaust system is described using FIG. 5 (A) and FIG. 5 (B). The exhaust system (280) for exhausting the atmosphere of the reaction tube (210) includes an exhaust pipe (281) communicating with the reaction tube (210) and is connected to the ore body (241) via an exhaust pipe connection part (242).

[0060] As shown in FIG. 5 (A), a vacuum pump (284) as a vacuum exhaust device is connected to the exhaust pipe (281) via a valve (282) as an opening / closing valve and an APC (Auto Pressure Controller) valve (283) as a pressure regulator (pressure regulating unit), and is configured to vacuum exhaust so that the pressure inside the reaction pipe (210) becomes a predetermined pressure (vacuum degree). The exhaust pipe (281), valve (282), and APC valve (283) are collectively referred to as the exhaust system (280). The exhaust system (280) is also called the processing room exhaust system. Additionally, the pump (284) may be included in the exhaust system (280).

[0061] The exhaust system (290) for exhausting the atmosphere of the sil-sil (217) includes an exhaust pipe (291) that is connected to the sil-sil (217) and communicates with the interior thereof.

[0062] A vacuum pump (294) serving as a vacuum exhaust device is connected to the exhaust pipe (291) via a valve (292) serving as an opening / closing valve and an APC valve (293), and is configured to allow vacuum exhaust so that the pressure inside the material chamber (217) becomes a predetermined pressure (vacuum degree). The exhaust pipe (291), valve (292), and APC valve (293) are collectively referred to as the exhaust system (290). The exhaust system (290) is also referred to as the material chamber exhaust system. Additionally, the pump (294) may be included in the exhaust system (290).

[0063] Next, using FIG. 6, a controller, which is a control unit (control means), will be described. The substrate processing device (10) includes a controller (600) that controls the operation of each part of the substrate processing device (10).

[0064] A schematic of the controller (600) is illustrated in FIG. 6. The controller (600) is configured as a computer equipped with a CPU (Central Processing Unit) (601), RAM (Random Access Memory) (602), a memory device (603) as a storage unit, and an I / O port (604). The RAM (602), memory device (603), and I / O port (604) are configured to exchange data with the CPU (601) via an internal bus (605). The transmission and reception of data within the substrate processing unit (10) is performed by the instruction of the transmission and reception instruction unit (606), which is also a function of the CPU (601).

[0065] A network transceiver (683) is installed in the controller (600) and connected to the upper device (670) via a network. The network transceiver (683) is capable of receiving information regarding the processing history or scheduled processing of the substrate (S) stored in the pod from the upper device (670).

[0066] The memory device (603) is composed of, for example, flash memory, HDD (Hard Disk Drive), etc. Within the memory device (603), a control program that controls the operation of the substrate processing device (10), a process recipe containing the sequence or conditions of substrate processing, etc., is stored so as to be readable.

[0067] In addition, the process recipe is a combination of steps in the substrate processing process described later, which is executed by the controller (600) to obtain a predetermined result, and functions as a program. Hereinafter, this process recipe and control program, etc., are collectively referred to simply as a program. Also, in this specification, when the word "program" is used, it may include only the process recipe, only the control program, or both. Additionally, the RAM (602) is configured as a memory area (work area) where programs or data read by the CPU (601) are temporarily stored.

[0068] The I / O port (604) is connected to each component of the substrate processing device (10).

[0069] The CPU (601) is configured to read and execute a control program from the memory device (603), and also to read a process recipe from the memory device (603) in accordance with the input of an operation command from the input / output device (681). The CPU (601) is configured to control the substrate processing device (10) to follow the contents of the read process recipe.

[0070] The CPU (601) includes a transmission / reception indicator (606). The controller (600) can be configured according to the present form by installing the program on the computer using an external storage device [e.g., a magnetic disk such as a hard disk, an optical disk such as a DVD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory] (682) that stores the aforementioned program. Furthermore, the means for supplying the program to the computer is not limited to supplying it via the external storage device (682). For example, the program may be supplied without interposing the external storage device (682) by using communication means such as the Internet or a dedicated line. In addition, the storage device (603) and the external storage device (682) are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. In addition, when the word "recording media" is used in this specification, it may include only the storage device (603), only the external storage device (682), or both.

[0071] Next, a process for forming a thin film on a substrate (S) using a substrate processing device (10) of the aforementioned configuration as a process of semiconductor manufacturing is described. In addition, in the following description, the operation of each part constituting the substrate processing device (10) is controlled by a controller (600).

[0072] Here, using FIG. 7, a film formation process is described for forming a film on a substrate (S) that includes a groove as a recess on the surface by using a first gas and a second gas and supplying them alternately.

[0073] (S102)

[0074] The pressure adjustment process (S102) for the material chamber is described. Here, the pressure inside the material chamber (217) is set to the same level as the pressure in the vacuum conveying chamber (217) adjacent to the material chamber (217). Specifically, the exhaust system (290) is operated to exhaust the atmosphere in the material chamber (217) so that the atmosphere in the material chamber (217) becomes a vacuum level.

[0075] (S104)

[0076] Next, the substrate loading process (S104) is described. When the material handling room (217) reaches a vacuum level, the transfer of the substrate (S) begins. When the substrate (S) arrives at the vacuum transfer room, the gate valve is opened, and the vacuum transfer robot loads the substrate (S) into the material handling room (217).

[0077] At this time, the substrate support (300) is kept in the transfer chamber (217), and the substrate (S) is transferred to the substrate support (300). When a predetermined number of substrates (S) are transferred to the substrate support (300), the vacuum transfer robot is withdrawn, and the substrate support (300) is raised by the vertical driving mechanism (400) to move the substrate (S) into the processing chamber inside the reaction tube (210).

[0078] In the movement to the reaction tube (210), the surface of the substrate (S) is positioned so as to be aligned with the height of the partition plate (226) and the partition plate (232).

[0079] (S106)

[0080] Next, the heating process (S106) is described. When a substrate (S) is introduced into the processing chamber inside the reaction tube (210), the pressure inside the reaction tube (210) is controlled to a predetermined pressure, and the surface temperature of the substrate (S) is controlled to a predetermined temperature. The temperature of the heater (211) is controlled so that the temperature of the substrate (S) is, for example, 100°C or higher and 1,500°C or lower, preferably 200°C or higher and 1,000°C or lower, and also preferably 400°C or higher and 800°C or lower. In addition, the pressure inside the reaction tube (210) can be considered to be, for example, 5 Pa to 100 kPa.

[0081] (S108)

[0082] Next, the film treatment process (S108) is described. The film treatment process of S108 is performed after the heating process (S106). In the film treatment process (S108), according to the process recipe, the following first to fourth steps are performed multiple times on a substrate (S) that includes a groove as a recess on its surface to form a predetermined film.

[0083] That is, in the first step, a first gas is supplied to the reaction tube (210), and in the second step, the atmosphere of the reaction tube (210) is exhausted along with the supply of an inert gas as a purge process, and in the third step, a second gas is supplied to the reaction tube (210), and in the fourth step, the atmosphere of the reaction tube (210) is exhausted along with the supply of an inert gas as a purge process. By performing an alternating supply process that repeats these first to fourth steps multiple times non-simultaneously, a predetermined film is formed on a substrate (S) having grooves on its surface.

[0084] For each substrate (S), a gas flow is formed in the upstream rectifier (214), the space on the substrate (S), and the downstream rectifier (215). At this time, since gas is supplied to the substrate (S) without pressure loss on each substrate (S), uniform processing between each substrate (S) becomes possible.

[0085] Additionally, it may be configured to correspond each upstream rectifier (214) and downstream rectifier (215) with a plurality of substrates (S). Doing so is advantageous in that it can reduce the number of parts. However, due to pressure between the plurality of substrates (S), turbulence occurs when gas collides with the side of the substrate, and the gas supply situation changes between separate substrates arranged above and below, variations in processing occur between the substrates (S). In particular, when turbulence occurs, there is a risk of gas retention occurring on the front side of the substrate (S), so gas decomposition proceeds on the front side of the substrate (S), and as a result, it accumulates on the edge side of the substrate (S). Therefore, the uniformity of processing within the substrate surface is reduced.

[0086] As a result, there is a possibility that deviations may occur in the film processing. Therefore, as in this embodiment, installing an upstream rectifier (214) and a downstream rectifier (215) corresponding to one substrate (S) is advantageous in that it reduces deviations in processing between substrates (S).

[0087] [1st Gas Supply, 1st Step]

[0088] The valve (254) is opened and the first gas is flowed into the gas supply pipe (251). The first gas is flow-regulated by the MFC (253) and supplied into the reaction pipe (210) via the upstream rectifier (214) from the gas supply structure (212). Then, it is exhausted via the space on the substrate (S), the downstream rectifier (215), the gas exhaust structure (213), and the exhaust pipe (281). At this time, the valve (258) may be opened and an inert gas, such as N2 gas, may be flowed into the gas supply pipe (255). At this time, to prevent the first gas from entering the gas supply pipe (261), the valve (268) may be opened and an inert gas may be flowed into the gas supply pipe (265).

[0089] At this time, the APC valve (283) is adjusted to set the pressure inside the reaction tube (210) to a pressure within the range of, for example, 1 Pa to 3,990 Pa. The supply flow rate of the first gas controlled by the MFC (253) is set to a flow rate within the range of, for example, 0.1 slm to 20 slm. Hereinafter, the temperature of the heater (211) is set to a temperature within the range of, for example, 100°C to 1,500°C, and heated between 400°C and 800°C. The time for supplying the first gas to the substrate (S) is set to a time within the range of, for example, 0.1 seconds to 1,000 seconds. The flow rate of the first gas is set to a flow rate within the range of, for example, 0.1 m / second to 100 m / second, preferably 0.5 m / second to 50 m / second, and also preferably 1 m / second to 20 m / second. The time it takes for the first gas to reach the substrate (S) is between 0.00001 seconds from the nozzle outlet, preferably 0.0001 seconds from the nozzle outlet, and also preferably 0.001 seconds from the nozzle outlet.

[0090] At this time, a first gas is supplied horizontally to the substrate (S) from the side of the substrate (S) through a gas supply structure (212) connected to the processing chamber. As the first gas, a gas in which at least two Si atoms are combined can be used, such as Si2Cl6 gas (hereinafter referred to as HCDS gas), which is a gas containing Si and Cl. That is, the first gas in an undissolved state is supplied horizontally to the surface of the substrate (S) from the side of the substrate (S). By this, the first gas is supplied into the groove, and the first gas is decomposed into a precursor by colliding with the wall (700) constituting the groove. The decomposed precursor is then attached to the inner wall of the wall constituting the groove.

[0091] Here, the distance from the gas supply structure (212) to the substrate (S) is set according to the time during which the first gas can be maintained in an undissolved state. That is, the distance from the gas supply structure (212) to the substrate (S) is set to a distance corresponding to at least the time of undissolved first gas. In other words, the distance until the first gas reaches the substrate (S) is the distance for attaching the precursor to the inner wall of the wall constituting the groove. Meanwhile, undissolved refers to a state in which a large amount of the supplied gas is not decomposed. It includes not only a state in which all the supplied gas is not decomposed, but also a state in which a predetermined amount of the supplied gas is decomposed and the remainder is not decomposed. The predetermined amount refers, for example, about 1% of the supplied gas.

[0092] Here, the distance from the gas supply structure (212) to the substrate (S) is at least the distance from the tip of the gas supply structure (212), such as the tip of the nozzle (223), to the substrate (S), and may be, for example, the distance from the tip of the nozzle (223) to the upstream edge of the substrate (S), the distance from the tip of the nozzle (223) to the center of the substrate (S), or the distance from the tip of the nozzle (223) to the downstream edge of the substrate (S).

[0093] For example, when HCDS gas is used as the first gas, HCDS gas in an undissolved state among the HCDS gas supplied into the reaction tube (210) is supplied from the side of the substrate (S), and as shown in FIG. 8, the HCDS gas is supplied into the groove and collides with the wall (700) constituting the groove. Due to this collision, the Si-Si bonds of the HCDS gas, Si2Cl6, are broken and decomposed into the precursor, SiCl2. Since SiCl2 is also a state in which a film is formed, it is also called an intermediate. The molecular size of the decomposed SiCl2 becomes smaller than that of HCDS, making it easier to adhere to the wall (700) constituting the groove. That is, by supplying HCDS gas in an undissolved state from the side of the substrate (S), the HCDS gas is supplied onto the surface of the substrate (S) in an undissolved state and collides with the wall (700) constituting the groove. Accordingly, HCDS gas is supplied in an undissolved state on the surface of the substrate (S), and within the groove, the HCDS gas is decomposed into SiCl2, and the decomposed SiCl2 is attached within the groove.

[0094] That is, when, for example, HCDS gas is used as the first gas, the Si bonds have a bonding energy such that they are severed by collision with the wall, so the number of bonds between Si bonds is severed by the impact colliding with the wall of the groove and decomposes into the precursor SiCl2. Meanwhile, if the first gas is decomposed upstream of the groove, the precursor (SiCl2) is generated upstream of the groove and forms a film around the groove, and voids are formed within the groove, which may worsen the step coverage. This is because the decomposed precursor has a high deposition rate (film formation speed) and is easy to adhere to the wall (700) that constitutes the groove.

[0095] That is, in this form, HCDS gas is supplied to the surface of the substrate (S) in a non-decomposed state and is configured to generate SiCl2 with a high deposition rate by colliding with the wall (700) inside the groove. As a result, a Si-containing film is formed that is easily delivered to the bottom of the groove and has improved step coverage performance.

[0096] In addition, as the first gas, a gas having the property that the amount of decomposition increases with the passage of time when the processing temperature and processing pressure are nearly constant is used. And as shown in FIG. 9, for example, the amount of decomposition of the first gas is within a predetermined range, and the region within the range up to the time (T) when the amount of decomposition of the first gas is less than or equal to a predetermined amount A is set as the region in which the first gas is in an undecomposed state, and the time from when the first gas is supplied until it reaches the substrate (S) is set. This time is the time during which SiCl2 can be attached to the inner wall of the groove. In addition, the processing temperature is set to a temperature that allows SiCl2 to be attached to the inner wall of the groove.

[0097] In addition, to suppress the decomposition rate of the first gas, the total pressure inside the reaction tube (210) when supplying the first gas may be set to a low voltage of, for example, 100 Pa or less, and the flow rate inside the reaction tube (210) may be increased to suppress the retention of the gas inside the reaction tube (210). For example, when supplying HCDS gas, the voltage is set so that the decomposition rate of the HCDS gas is within 1%. Or, the partial pressure of SiCl2 decomposed from the HCDS gas is set so that it is 0.1 Pa or less. By doing so, the step coverage performance is improved.

[0098] In addition, the first gas is supplied at a flow rate capable of adsorbing (attaching) SiCl2 to the inner wall of the groove. As a result, step coverage performance is improved because SiCl2 can be reliably adsorbed to the inner wall of the groove.

[0099] In this case, when an L-shaped nozzle extending vertically with respect to the substrate (S) is used as the gas supply unit, the pressure inside the nozzle increases, and the decomposition of the gas may proceed until it is supplied to the substrate (S). In addition, in the case of a configuration in which an exhaust port for exhausting the gas inside the reaction tube is provided on the lower side of the reaction tube, the pressure loss of the gas flow increases because the gas flows vertically inside the reaction tube, and the pressure inside the reaction tube increases, and the decomposition of the gas may proceed. In addition, in the case of a configuration in which gas remains between the inner wall of the top plate of the reaction tube and the top plate of the substrate support, the decomposition of the gas may proceed.

[0100] In addition, to improve step coverage performance, a sufficient amount of raw gas (supply partial pressure × supply time) must be supplied to the substrate (S) containing the groove. Furthermore, when using a device that includes a configuration with a long gas residence time inside the furnace, supplying raw gas at a high partial pressure results in the decomposition of the raw gas compared to supplying it at a low partial pressure. Therefore, although step coverage performance is improved by supplying raw gas at a low partial pressure, supplying raw gas at a low partial pressure requires extending the supply time to ensure a sufficient amount of exposure. In other words, there was a trade-off between productivity and step coverage performance.

[0101] In the present form, when, for example, HCDS gas is used as the first gas, reaction by-products such as Cl or HCl can be removed by raising the temperature of the substrate (S) to a high temperature, and it is possible to improve step coverage performance. However, when the temperature of the substrate (S) is raised to a high temperature, the decomposition of HCDS gas proceeds.

[0102] According to the present embodiment, it is possible to shorten the time for the first gas to reach the substrate (S), and even when the temperature of the substrate (S) is raised to a high temperature, it is possible to improve step coverage performance while suppressing the decomposition of the raw gas on the surface of the substrate (S).

[0103] That is, according to the substrate processing device (10) of the present type, even when the raw material gas is supplied at a high partial pressure, it is possible to shorten the time for the first gas to reach the substrate (S), and it is possible to improve productivity and step coverage performance while suppressing the decomposition of the raw material gas on the surface of the substrate (S).

[0104] In addition, in this form, by making the gas exhaust structure (213) a transverse exhaust structure that exhausts gas from the transverse direction of the substrate (S), the pressure loss within the reaction tube (210) can be reduced and the surface-to-surface uniformity of the substrate (S) can be improved.

[0105] In addition, in this form, by configuring the width of the opening connected to the exhaust side of the reaction tube (210) to be wide, the retention of gas is suppressed and the vortex of the gas flow is reduced, thereby suppressing the decomposition of gas on the surface of the substrate (S).

[0106] In addition, the top plate of the substrate support may be removed, and the substrate (S) may be placed directly below the inner wall of the top plate of the reaction tube (210). By doing so, the retention of gas between the top plate of the substrate support and the inside of the reaction tube is suppressed, making it possible to suppress the decomposition rate of the first gas within a predetermined range and to suppress the decomposition of the first gas on the surface of the substrate (S). In addition, the raw material gas may be supplied with the gas injection angle of the nozzles (223, 224) installed in multiple stages on the side of the reaction tube (210) offset from the center of the reaction tube (210).

[0107] [Purge, Step 2]

[0108] After the supply of the first gas is started and a predetermined time has elapsed, the valve (254) is closed and the supply of the first gas is stopped. At this time, the valves (258, 268) are opened and an inert gas as a purge gas is supplied into the gas supply pipe (255, 265), and the valve (282) of the exhaust pipe (281) and the APC valve (283) are opened, and the inside of the reaction pipe (210) is vacuum exhausted by the vacuum pump (284). By doing so, the reaction between the first gas and the second gas in the gas phase present in the reaction pipe (210) can be suppressed.

[0109] [Second gas supply, third step]

[0110] After starting the purging and after a predetermined time has elapsed, valves (258, 268) are closed and valve (264) is opened to flow a second gas into the gas supply pipe (261). The second gas is flow-regulated by the MFC (263) and supplied into the reaction pipe (210) via the upstream rectifier (214) from the gas supply structure (212). Then, it is exhausted via the space on the substrate (S), the downstream rectifier (215), the gas exhaust structure (213), and the exhaust pipe (281). At this time, valve (268) may be opened simultaneously to flow an inert gas, such as N2 gas, into the gas supply pipe (265). At this time, to prevent the second gas from entering the gas supply pipe (251), valve (258) may be opened to flow an inert gas into the gas supply pipe (255).

[0111] At this time, the APC valve (283) is adjusted to set the pressure inside the reaction tube (210) to a pressure within the range of, for example, 1 Pa to 3,990 Pa. The supply flow rate of the second gas controlled by the MFC (263) is set to a flow rate within the range of, for example, 0.1 slm to 100 slm. The time for supplying the second gas to the substrate (S) is set to a time within the range of, for example, 0.1 seconds to 1,000 seconds. The flow rate of the second gas supplied to the substrate (S) is set to a flow rate within the range of, for example, 0.1 m / second to 100 m / second.

[0112] At this time, a second gas is supplied to the substrate (S) from the side of the substrate (S) via a gas supply structure (212). Here, the second gas may be a gas different from the first gas and a gas that reacts with the first gas, such as an N-containing gas, such as NH3 gas. That is, the second gas is supplied to the surface of the substrate (S) from the side of the substrate (S). Then, the second gas is supplied into the groove and reacts with a precursor attached to the wall (700) constituting the groove, so that a desired film is formed on the substrate (S) containing the groove. Specifically, on the surface of the substrate (S), the NH3 gas reacts with the HCDS gas, and the NH3 gas supplied into the groove reacts with SiCl2 attached to the wall (700) constituting the groove, and a silicon nitride (SiN) film is formed with improved step coverage performance and suppressed voids.

[0113] Here, when NH3 gas is used as the second gas, when HCDS gas and NH3 gas react, NH2 bonds are formed on the film. For example, when the HCDS supplied next reacts with NH2, Cl or hydrogen chloride (HCl) is produced. When this Cl and HCl remain between SiCl2 and the inner wall of the groove, Cl and HCl inhibit SiCl2 from adhering to the inner wall of the groove. Therefore, it is set as a temperature that removes by-products such as NH2 generated in the groove of the substrate (S), and a temperature at which the decomposition of the first gas, HCDS, is not promoted, for example, a temperature at which NH terminals are removed. Additionally, NH3 gas is supplied from the side of the substrate (S) during a time when HCDS is not decomposed and SiCl2 is not generated.

[0114] [Fuzzy, Step 4]

[0115] After the supply of the second gas is started and a predetermined time has elapsed, the valve (264) is closed and the supply of the second gas is stopped. At this time, the valves (258, 268) are opened and an inert gas as a purge gas is supplied into the gas supply pipes (255, 265), and the valve (282) of the exhaust pipe (281) and the APC valve (283) are opened so that the inside of the reaction pipe (210) is vacuum exhausted by the vacuum pump (284). By doing so, the reaction between the first gas and the second gas in the gas phase present in the reaction pipe (210) can be suppressed.

[0116] (Perform a prescribed number of times)

[0117] A film of a predetermined thickness is formed on a substrate (S) containing a groove by performing a cycle of performing the aforementioned first to fourth steps in sequence non-simultaneously at least once (N times). Here, for example, a SiN film is formed.

[0118] (S110)

[0119] Next, the substrate removal process (S110) is described. In S110, the processed substrate (S) is removed from the material room (217) in the reverse order of the aforementioned substrate receiving process (S104).

[0120] (S112)

[0121] The determination (S112) is explained further. Here, it is determined whether a predetermined number of substrates have been processed. If it is determined that the predetermined number of processing has not been processed, the process returns to the substrate receiving process (S104) to process the next substrate (S). If it is determined that the predetermined number of processing has been processed, the processing is terminated.

[0122] In addition, although the formation of the gas flow was described as horizontal above, it is preferable for the main stream of gas to be formed in a horizontal direction overall; however, a gas flow that diffuses in a vertical direction is also acceptable as long as it does not affect the uniform processing of multiple substrates.

[0123] Furthermore, although expressions such as "same degree," "equal," and "same" are used above, it goes without saying that these include substantially the same thing.

[0124] (Other embodiments)

[0125] Although embodiments of the present form have been specifically described above, they are not limited thereto, and various modifications are possible within the scope of not departing from the gist thereof.

[0126] In addition, for example, in each of the aforementioned embodiments, the case in which a film is formed on a substrate (S) using a first gas and a second gas in the film deposition process performed by the substrate processing device was given as an example, but the present embodiment is not limited thereto. That is, it is acceptable to form a different type of thin film using a different type of gas as the processing gas used for the film deposition process. Furthermore, even in cases where three or more types of processing gases are used, the present embodiment can be applied as long as the film deposition process is performed by supplying them alternately.

[0127] In addition, for example, in each of the aforementioned embodiments, film deposition was exemplified as a process performed by a substrate processing device, but the present embodiment is not limited thereto. That is, in addition to the film deposition exemplified in each embodiment, the present embodiment can be applied to film deposition processes other than the thin films exemplified in each embodiment. Furthermore, although the present embodiment describes a device for processing multiple substrates by stacking them, it is not limited thereto and can be applied to a single-wafer device for processing substrates one by one. In addition, it is possible to replace a part of the configuration of one embodiment with a part of another embodiment, and it is also possible to add a part of another embodiment to a part of one embodiment. Furthermore, it is possible to add, delete, or replace a part of the configuration of each embodiment with another configuration. Explanation of the symbols

[0128] S: Substrate 10: Substrate processing device 210: Reaction tube 600: Controller

Claims

Claim 1 A process comprising: (a) supplying a raw material gas to a substrate from the side of a substrate having a concave portion on its surface; and (b) supplying a reaction gas to the substrate, wherein a process comprising performing a cycle a predetermined number of times to form a film on the substrate, wherein in (a), the raw material gas is supplied under conditions in which the amount of decomposition of the raw material gas increases over time when the processing temperature and processing pressure are constant, and wherein the raw material gas supplied in (a) is decomposed by colliding the gas in which the decomposed raw material gas is in a state of being 0% or more and within 1% with the inner wall of the concave portion to generate an intermediate, and wherein the intermediate is attached to the inner wall of the concave portion, and wherein in (b), the intermediate attached to the concave portion is reacted with the reaction gas. Claim 2 A treatment method according to claim 1, wherein the raw gas is decomposed by colliding with the wall constituting the above part. Claim 3 A treatment method according to claim 1, wherein the raw material gas has binding energy that decomposes by colliding with the wall constituting the above part. Claim 4 A processing method according to claim 1, wherein the raw gas contains Si-Si bonds, and the Si-Si bonds are cut by collision with a wall constituting the part. Claim 5 A treatment method according to claim 1, wherein the flow rate of the raw material gas is a flow rate that attaches the intermediate to the inner wall of the portion. Claim 6 A processing method according to claim 1, wherein the time until the raw material gas reaches the substrate is the time for the intermediate to adhere to the inner wall of the portion. Claim 7 A processing method according to claim 1, wherein the distance until the raw material gas reaches the substrate is the distance for attaching the intermediate to the inner wall of the portion. Claim 8 A processing method according to claim 1, wherein the raw material gas is supplied from a gas supply structure communicating with the space where the substrate exists, and the distance from the gas supply structure to the substrate is set according to the time during which the undissolved state can be maintained. Claim 9 A processing method according to claim 1, wherein the raw material gas is supplied from a gas supply structure communicating with the space where the substrate exists, and the distance from the gas supply structure to the substrate is a distance for attaching the intermediate to the inner wall of the portion. Claim 10 A processing method according to claim 1, wherein the temperature of the substrate when supplying the raw material gas is a temperature at which the intermediate is attached to the inner wall of the portion. Claim 11 A treatment method according to claim 1, wherein the raw material gas is a gas in which at least two Si atoms are bonded. Claim 12 In claim 11, the above decomposition is a processing method in which the bonds of the Si atoms are severed. Claim 13 A treatment method according to claim 1, wherein the raw material gas is a gas containing silicon and chlorine. Claim 14 A treatment method according to claim 1, wherein the raw material gas is hexachlorodisilamine. Claim 15 A processing method according to claim 1, wherein the source gas and the reaction gas are alternately supplied to the substrate, and the temperature of the substrate is a temperature at which NH terminals generated within a portion of the substrate are defused when the source gas and the reaction gas are alternately supplied, and the temperature is set such that the decomposition of the source gas is not promoted. Claim 16 A treatment method according to claim 1, wherein the flow rate of the raw material gas is 0.1 m / sec to 100 m / sec. Claim 17 A processing method according to claim 1, wherein the time for the raw material gas to reach the substrate is between 0.00001 seconds from the nozzle outlet. Claim 18 In claim 1, the processing method wherein the substrate is heated between 100°C and 1,500°C. Claim 19 A processing method according to claim 1, wherein the total pressure when supplying the raw material gas is set such that the decomposition rate of the raw material gas is within 1% or the partial pressure of the intermediate is 0.1 Pa or less. Claim 20 A processing method according to claim 1, wherein when supplying the raw material gas, the gas injection angle of the nozzles installed in multiple stages on the side of the reaction tube is offset from the center of the reaction tube. Claim 21 A method for manufacturing a semiconductor device comprising: (a) a process of supplying a raw material gas to a substrate from the side of a substrate including a recess on its surface; and (b) a process of supplying a reaction gas to the substrate, wherein the raw material gas is supplied under conditions in which the amount of decomposition of the raw material gas increases over time when the processing temperature and processing pressure are constant, and the raw material gas is decomposed by colliding the gas in which the decomposed raw material gas is in a state of being 0% or more and within 1% among the raw material gas supplied in (a) with the inner wall of the recess to generate an intermediate, and the intermediate is attached to the inner wall of the recess, and (b) the intermediate attached to the recess is reacted with the reaction gas. Claim 22 A raw material gas supply system for supplying raw material gas to a substrate from the side of a substrate including a recess on its surface; a reaction gas supply system for supplying reaction gas to the substrate; a heating unit for heating the substrate; and an exhaust system for controlling the pressure in the space where the substrate exists. A processing apparatus comprising a control unit configured to enable the control of the raw gas supply system, the reaction gas supply system, the heating unit, and the exhaust system, wherein the processing apparatus comprises: (a) a process of supplying a raw gas to the substrate and (b) a process of supplying a reaction gas to the substrate, thereby performing a process of forming a film on the substrate by performing a cycle a predetermined number of times, wherein in (a), the raw gas is supplied under conditions in which the amount of decomposition of the raw gas increases with the passage of time when the processing temperature and processing pressure are constant, and the raw gas is decomposed by colliding the gas in which the decomposed raw gas is in a state of being 0% or more and within 1% among the raw gas supplied in (a) with the inner wall of the recess to generate an intermediate, and the intermediate is attached to the inner wall of the recess, and in (b), the raw gas supply system, the reaction gas supply system, the heating unit, and the exhaust system are controlled to react the intermediate attached to the recess. Claim 23 A program recorded on a recording medium, wherein the steps of: (a) supplying a raw material gas to a substrate from the side of a substrate including a recess on its surface; and (b) supplying a reaction gas to the substrate, by performing a cycle a predetermined number of times; wherein in (a), the raw material gas is supplied under conditions in which the amount of decomposition of the raw material gas increases with the passage of time when the processing temperature and processing pressure are constant; wherein, among the raw materials supplied in (a), the gas in which the decomposed raw material gas is in a state of being 0% or more and within 1% collides with the inner wall of the recess to decompose the raw material gas to generate an intermediate, and attach the intermediate to the inner wall of the recess; and (b) reacting the intermediate attached within the recess with the reaction gas, and executing the steps of the reaction gas with the intermediate attached within the recess using a computer.

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